WO2016038373A1 - Composition d'encre - Google Patents

Composition d'encre Download PDF

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Publication number
WO2016038373A1
WO2016038373A1 PCT/GB2015/052618 GB2015052618W WO2016038373A1 WO 2016038373 A1 WO2016038373 A1 WO 2016038373A1 GB 2015052618 W GB2015052618 W GB 2015052618W WO 2016038373 A1 WO2016038373 A1 WO 2016038373A1
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WO
WIPO (PCT)
Prior art keywords
ink
absorber
present
light
colorant
Prior art date
Application number
PCT/GB2015/052618
Other languages
English (en)
Inventor
Claire Bourdin
Jonathan Morgan
Original Assignee
Domino Uk Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Domino Uk Limited filed Critical Domino Uk Limited
Priority to JP2017534014A priority Critical patent/JP2017534740A/ja
Priority to CN201580049288.4A priority patent/CN107075287A/zh
Priority to US15/510,354 priority patent/US10583666B2/en
Priority to EP15766210.7A priority patent/EP3191555A1/fr
Publication of WO2016038373A1 publication Critical patent/WO2016038373A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/14—Printing inks based on carbohydrates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00—Thermometers giving results other than momentary value of temperature
    • G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time

Definitions

  • the present invention relates to an inkjet ink comprising a photo-chromic colorant and a UV absorber.
  • the ink may be used as a time-temperature indicator and is particularly useful in packaging food and/or drink to provide an
  • the invention relates to the printing of indicating codes or marks which vary in colour as a function of temperature over time (time-temperature indicator) .
  • time-temperature indicator time-temperature indicator
  • temperature is one of the most important factors influencing the rate of microbial growth in and the amount of physical and chemical deterioration in food products. It is therefore useful to report the time- temperature history along the cold chain, so that the consumer can make an informed choice about the food products they choose, and the suppliers of food products can use a less conservative set of assumptions in setting use-by dates.
  • a model time-temperature indicator would be a simple, cost-effective and provide an easily understood indication that the temperature and time history of the food product means that it is of good quality and safe to
  • a common approach to producing time-temperature indicator technology is to make use of a reversible photo-activated reaction that yields a colour change upon activation.
  • Such materials have an initial colour, which is changed when activated with light of a suitable wavelength and then revert to their original colour over time.
  • the rate of change of colour of the photo-activated compound in such indicators can be influenced by exposed temperature.
  • WO 2005/075978 relates to a photo-chromic colorant
  • temperature indicator is then optionally provided with a protector, which prevents the renewed photo-induced
  • the protector may be a protective coating or a laminate that comprises a filter, for example a polypropylene colour filter, which filters out certain wavelength ranges.
  • an inkjet ink comprising:
  • the present inventors have surprisingly found that the incorporation of a UV absorber within the inkjet ink
  • the UV absorber also does not substantially affect the colour change of the indicator over time.
  • a cartridge comprising the ink as described herein.
  • a time temperature indicator comprising the ink and/or the deposit as described herein.
  • a method of producing the ink as described herein comprising mixing a photo-chromic colorant and a UV absorber.
  • activation refers to the chemical reaction caused by UV light which changes the initial colour of the photo-chromic colorant.
  • a spiropyran activated by UV light i.e, a UV light
  • photomerocyanine has a different colour to the deactivated spiropyran due to the ring opening chemical reaction caused by the UV light.
  • reverse reaction refers to the chemical reaction of the colorant from the activated form to the deactivated form.
  • the reverse reaction refers to the thermally assisted ring closing reaction of the photomerocyanine form to the spiropyran form.
  • the term “fading” refers to the colour change of the photo-chromic colorant as it undergoes the reverse reaction, thermally assisted, from the activated form to the deactivated form.
  • the colour of a photomerocyanine will fade as it undergoes the thermally assisted ring closing reaction to the colourless spiropyran form.
  • the rate of fading corresponds to the rate of the reverse reaction, which depends on the temperature the colorant is exposed to.
  • recharging refers to the re-activating of an at least partially faded photo-chromic colorant by ambient and/or outdoor UV light.
  • an inkjet ink comprising:
  • the present inventors have now surprisingly found that the incorporation of a UV absorber within the inkjet ink prevents and/or reduces the recharging of the ink when exposed to ambient light, without, as one would expect, preventing the initial activation of the photo-chromic colorant and without substantially affecting the colour change of the indicator over time.
  • the activated ink is therefore a reliable time-temperature indicator as it can provide accurate information regarding the amount of time that has elapsed and the temperature which it has experienced since its initial activation.
  • the ink is provided, for example, as a deposit on a food packaging and activated at the time of sealing food therein, it therefore also provides a reliable indication of the quality of the food.
  • Providing the UV absorber within the inkjet ink obviates the need for a further protective layer atop the time temperature indicator.
  • the UV absorber has an absorbance peak broader than the absorbance peak of the deactivated photo-chromic colorant (e.g. a spiropyran) .
  • the deactivated photo-chromic colorant e.g. a spiropyran
  • activation of the ink reduces the absorbance peak of the activated colorant (e.g. the photomerocyanine ) but surprisingly does not prevent
  • the UV absorber then preferably prevents and/or reduces significant
  • the photochemical process can be monitored visually, by the human eye, for example.
  • the rates of the reversible reaction and the corresponding colour change of the photo-chromic colorant may be affected by the respective concentrations of the colorant and the UV absorber, as well as by any substrate the ink is printed on.
  • the life-time or ' shelf-life ' of the time temperature indicator/ink as described herein may be tuned to specific foods by varying the concentration of the ink components and/or varying the substrate.
  • the photo-chromic colorant is a spiroaromatic compound.
  • Spiroaromatic compounds are known to be suitable as indicator compounds in TTI systems and are discussed in WO 2005/075978.
  • Spiroaromat ic compounds consist structurally of two carbocycles connected through a single carbon atom from which four extending bonds are bonding other carbon or heteroatoms. Of the four bonds, extending from, the spiro carbon centre, at least one is to a
  • the colorant is a spiropyran.
  • Spiropyrans are one class of spiroaromat ic compounds. Spiropyrans comprise a pyran ring linked by a spiro carbon to a heterocyclic ring .
  • Irradiation of the colourless spiropyran with UV light causes heterolytic cleavage of the C-0 bond forming the ring-opened coloured species, often called the "merocyanine form 'which can take on a cis-(l, 2), trans- (1, 3) or the ortho-quinoidal form.
  • the pyran ring is usually a
  • the spiropyran is selected from 1,3,3- trimethylindolino-6 ' -nitrobenzopyrylospiran (also called 1 ' , 3 ' , 3 ' -trimethyl-6 -nitrospiro [1 ( 2H) -benzopyran-2 ,2'- indoline) , 1, 3-dihydro-l, 3, 3-trimethylspiro [ 2H-indole-2 , 3 '- [ 3H ] naphtho [ 2 , 1-b] [ 1 , 4 ] oxaz ine ] , 1 ' , 3 ' -dihydro-8-methoxy- 1 ' , 3 ' , 3 ' -trimethyl-6 -nitrospiro [ 2H-l -benzopyran-2 , 2 ' - ( 2H) - indole], 3 , 3-diphenyl-3H-naphtho [ 2 , 1-b] pyran, or
  • the colorant is present in an amount of from 0.5 to 10 wt %, based on the total weight of the ink. More preferably, the colorant is present in an amount of from 0.5 to 9 wt %, or from 1 to 8 wt %, or from 2 to 7 wt %, or from 3 to 6 wt %, based on the total weight of the ink. Most preferably the colorant is present in an amount of from 4 to 6 wt %, or about 5 wt %, based on the total weight of the ink .
  • UV light absorbers are widely known and commercially available.
  • the UV absorber is an acrylic resin and/or a styrene maleic anhydride copolymer.
  • the amount (e.g. at least 4 wt %, or at least 5 wt %, or at least 6 wt %, or at least 7 wt %, or at least 8 wt %, or at least 9 wt % based on the total weight of the ink) of the UV absorber is high enough to prevent the photo- chromic colorant (and therefore the ink itself) from
  • the amount (e.g. 15 wt % or less, or 12 wt % or less, or 11 wt % or less, or 11 wt % or less based on the total weight of the ink) of UV absorber is low enough to allow the temperature of the activated photo-chromic
  • the UV absorber is present in an amount low enough to allow the photo-chromic colorant to be activated when initially exposed to UV light.
  • the UV absorber is present in an amount of from 4 to 15 wt %, based on the total weight of the ink. More preferably, the UV absorber is present in an amount of from 5 to 12 wt %, or from 6 to 12 wt%, or from 7 to 11 wt%, or from 8 to 11 wt % based on the total weight of the ink.
  • the UV absorber is present in an amount of from 9 to 11 wt %, or about 10 wt%, based on the total weight of the ink.
  • the ink further comprises a solvent.
  • the solvent preferably complies with food packaging regulations and substantially/completely dissolves the photo-chromic
  • the solvent comprises a volatile organic solvent.
  • the solvent comprises a ketone, more preferably a ketone having four carbon atoms. More preferably still, the solvent comprises butan-2-one
  • MEK methylethyl ketone
  • CIJ continuous inkjet
  • the solvent is present in an amount of from 60 to 90 wt %, or from 65 to 85 wt %, based on the total weight of the ink. More preferably, the solvent is present in an amount of from 70 to 80 wt %, or about 75 wt %, based on the total weight of the ink.
  • the ink further comprises a binder.
  • Suitable binders include polyamide resins, polyurethane resins, rosin ester resins, acrylic resins, polyvinyl butyral resins, polyesters, phenolic resins, vinyl resins,
  • polystyrene/polyacrylate copolymers cellulose ethers, cellulose acetates, cellulose nitrate resins, polymaleic anhydrides, acetal polymers, polystyrene/polybutadiene copolymers, polystyrene/polymethacrylate copolymers,
  • binders are commercially available.
  • the binder is a cellulose resin and/or a rosin ester resin. More preferably, the binder is a
  • the binder is present in an amount of from 5 to 15 wt %, or from 7 to 14 wt %, or from 8 to 12 wt %, based on the total weight of the ink. More preferably, the binder is present in an amount of from 9 to 11 wt %, or about 10 wt %, based on the total weight of the ink.
  • the ink further comprises an additive.
  • the additive is a polyether siloxane copolymer.
  • the additive is present in an amount of from 0.1 to 2 wt %, or from 0.2 to 1.8 wt %, or from 0.4 to 1.6 wt %, or from 0.5 to 1.5 wt %, based on the total weight of the ink. More preferably, the additive is present in an amount of from 0.7 to 1.3 wt %, or from 0.8 to 1.2 wt %, or from 0.9 to 1.1 wt %, or about 1 wt %, based on the total weight of the ink.
  • the ink further comprises a salt. Providing a salt is advantageous because it improves the conductivity of the CIJ ink.
  • the salt is an ammonium salt and/or a bromide salt. More preferably, the salt is an ammonium salt.
  • Ammonium salts are particularly suitable for food packaging applications .
  • the salt is present in an amount of from 0.5 to 5 wt %, or from 0.8 to 4 wt %, or from 1 to 3 wt %, based on the total weight of the ink. More preferably, the salt is present in an amount of from 1.5 to 2.5 wt %, or about 2 wt %, based on the total weight of the ink. The amount should be as low as possible, for example, 5 wt % or lower, or 3 wt % or lower, or 2.5 % or lower, to prevent affecting the adhesion properties of the ink onto the substrate.
  • the ink has a viscosity of from 2 to 6 cP, or from 2.5 to 5.5 cP, or from 3 to 5 cP, at 25 °C. More preferably, the ink has a viscosity of from 3.5 to 4.5 cP, or about 4 cP, at 25 °C.
  • the viscosity of the ink may be measured using a viscometer such as a Brookfield DV-II+ viscometer or a rheometer.
  • the ink has a conductivity ( ⁇ ) of more than 450 pS/cm, or of more than 500 pS/cm, more preferably of more than 550 pS/cm.
  • the ink has a conductivity ( ⁇ ) of from 450 pS/cm to 5,000 pS/cm, or of from 500 pS/cm to 3,000 pS/cm, or of from 550 pS/cm to 2,000 pS/cm.
  • Providing an ink with the above viscosity and/or conductivity is advantageous because these properties are particularly favourable for use in CIJ technologies.
  • the article comprises food packaging and/or drink packaging. More preferably, the article comprises food packaging.
  • a cartridge comprising the ink as described herein.
  • time temperature indicator comprising the ink and/or the deposit as described herein.
  • any suitable substrate may be printed in accordance with the invention.
  • suitable substrates include porous substrates such as uncoated paper, semi-porous substrates such as aqueous coated paper, clay coated paper, silica coated paper, UV overcoated paper, polymer overcoated paper, and varnish overcoated paper, and non-porous substrates such as hard plastics, polymer films, polymer laminates, metals, metal foil laminates, glass, and ceramics.
  • the paper substrates may be thin sheets of paper, rolls of paper, or cardboard. Plastics, laminates, metals, glass, and ceramic substrates may be in any suitable form such as in the form of bottles or containers, plates, rods, cylinders, etc.
  • the substrate comprises food packaging and/or drink packaging. More preferably, the substrate comprises food packaging.
  • the UV light has a wavelength of from 300 to 450 nm, or from 325 to 425 nm, or from 340 to 410 nm. More preferably, the UV light has a wavelength of from 350 to 400 nm, or from 360 to 400 nm. Alternatively, preferably, the UV light has a wavelength of 350 to 380 nm, or from 360 to 370 nm, or about 365 nm. Alternatively, preferably, the UV light has a wavelength of 380 to 410 nm, or from 390 to 400 nm, or about 395 nm. Preferably the UV light is provided at an intensity of at least 1.5 W/cm 2 , or of at least 1.75 W/cm 2 . More preferably the UV light is provided at an intensity of at least 2 W/cm 2 , or of at least 2.2 W/cm 2 .
  • the UV light is provided at an intensity of from 1.5 to 3 W/cm 2 , or from 1.75 to 2.5 W/cm 2 , or from 2 to 2.4 W/cm 2 , or about 2.25 W/cm 2 .
  • providing the UV light to the ink as described herein at such wavelengths and/or intensities is advantageous because it is thought to activate the photo-chromic colorant without instead being completely absorbed by the UV absorber alone.
  • the UV light is provided to the ink and/or deposit at a distance of from 0.5 to 1,000 mm away from the ink and/or deposit, more preferably from 0.5 to 500 mm away from the ink and/or deposit, or from 0.5 to 250 mm away from the ink and/or deposit, most preferably from 1 to 100 mm away from the ink and/or deposit, or from 10 to 50 mm away from the ink, or about 20 mm away from the ink.
  • the UV light is provided by one or more UV light emitting diodes (LEDs) and/or one or more mercury arc lamps.
  • LEDs UV light emitting diodes
  • a mercury arc lamp with a maximum power 477 W could be used to activate the ink at 30%, 40% or 50% of its maximum power.
  • the colour of the activated ink may be fainter than an ink activated by a UV LED. Therefore, more preferably, the UV light is provided by one or more UV LEDs .
  • the ink is provided by inkjet printing.
  • the ink is provided or printed (e.g. inkjet printed) as a "best before date", particularly in the case of the substrate comprising food and/or drink packaging.
  • a "best before date” is advantageous because it provides a safety net i.e. it preferably prevents a false positive from the time temperature indicator.
  • the method comprising mixing a photo-chromic colorant and a UV absorber.
  • the inkjet ink is formulated by combining the components using methods known in the art.
  • the use of the ink as described herein as a time temperature indicator is provided.
  • Figure 1 shows the life-time of an ink as described herein and the rate at which it fades at 8°C.
  • Figure 2 shows the rate at which the printed ink fades on PET substrate at 8°C.
  • Figure 3 shows a comparison between an ink of the present invention and an ink without a UV absorber, showing the colour changes observed once the ink with the UV absorber and the ink without the UV absorber are exposed to ambient light .
  • Figure 4 shows the life-times of an ink as described herein at different temperatures and on different substrates.
  • Figures 5 and 6 show the life-times of three inks as described herein at different temperatures and on different substrates and the effect thereon of the concentration of the UV absorber.
  • Figure 7 shows the effect of varying the concentration of binder (polymer) or additives on the the shelf-life of the TTI ink on a specific substrate.
  • Figure 8 shows the shelf-lives of three inks of the present invention on the same and different substrates.
  • the ink did not contain a UV absorber and so the colorant was not protected from UV light.
  • the colour coordinates of the ink were recorded by a spectroeye before activation by UV light, and at 0, 1, 2, 3, 5, 7, 9, 15, 20 and 30 days after activation.
  • the ink was not subjected to UV or ambient light during this time and was kept at 8°C.
  • ⁇ 00 V[(dL/S L ') 2 + (dC'/S c ') 2 + (dH'/S H ') 2 + R T dC'/S c ' dH'/S H '] (Formula I)
  • T 1 - 0.17 cos (h' avg-30°) + 0.24 cos(2h' a vg ) + 0.32
  • R T -2V[C' avg 7(C' avg 7 + 25 7 )] . sin [60°. exp (- [ (h ' avg -275 ° ) / 25° ] 2 )]
  • L 2 , a 2 , b 2 , C 2 and h 2 are colour space measurements of the sample at a certain time after UV activation
  • Li, ai, bi, Ci and hi are colour space measurements of the sample after activation by UV lamp.
  • Example 1 the first value of ⁇ 0 ⁇ (dE) obtained was considered as 100%, and colour loss (fading) was plotted against time.
  • the results are shown in Figure 1 and show that, in 25 days, the colour of the colorant faded to around 10% of its colour after initial activation, i.e around 90% of its colour was lost.
  • Kept at 8°C the colorant may be used to provide an indication of the time lapsed after its initial activation, up to at least 25 days. The same is true at other temperatures. At higher temperatures, the colour of the colorant will fade faster than at lower temperatures .
  • the time-temperature indicator ink is prepared by addition of CAB-551-0.01 and Foralyn 110 as binders, TegoGlide 410 as additive, tert-butyl ammonium nitrate as salt, and
  • Joncryl682 as UV absorber to the solvent butan-2-one. Once dissolved, 1,3, 3-trimethylindolino-6 ' -nitrobenzopyrylospiran used as photochromic material was added to the solution.
  • the ink is then printed by a CIJ printer as a rectangle on a polyethylene terephthalate (PET) substrate.
  • PET polyethylene terephthalate
  • the performance of the ink of Example 2 was compared to an ink without a UV absorber therein.
  • the photo-chromic colorant in the respective inks was 1 , 3 , 3-trimethylindolino- 6 ' -nitrobenzopyrylospiran .
  • the two inks were printed onto a plastic (polyethylene terephthalate (PET)) substrate and were tested on their resistance to being recharged under outdoor/ambient UV light.
  • PET polyethylene terephthalate
  • the respective inks were kept in the dark (i.e. no exposure to UV / ambient light) for 34 days at 8°C. During this time, the colour change from initial activation was recorded using a spectroeye. Both inks faded as the colorant molecule went from the photomerocyanine form to the colourless spiropyran form, i.e. the ink became deactivated.
  • absorber does not recharge up to its original colour, and there is a visual noticeable difference of colour between the colour after activation and the colour after the TTI is subjected to outdoor light.
  • the ink appears to slightly recharge up to around 10 minutes after exposure to a colour which is still similar to its colour after 34 days in the dark (dEoo ⁇ 2.5) .
  • the ink does not recharge to its colour immediately after its initial activation by UV lamp.
  • the ink containing the UV absorber tends to heat up, promoting the ring-closing reaction whilst the UV absorber protects the colorant from substantial ring-opening. As a result, the equilibrium is pushed towards the reverse reaction (ring-closure) .
  • the ink without UV absorber therefore provides a false positive as it no longer reliably indicates the time and temperature since activation.
  • the ink with the UV absorber does not recharge by a significant amount in UV light and fades in a predictable manner. It is therefore suitable for use as a time temperature indicator.
  • Example 2 The ink of Example 2 was printed on to a variety of
  • Example 2 In addition to the ink of Example 2 (hereafter "Ink 1"), two further time-temperature indicator inks, "Ink 2" and “Ink 3" were prepared by addition of CAB-551-0.01 and Foralyn 110 as binders, TegoGlide 410 as additive, tert-butyl ammonium nitrate as salt, and Joncryl682 as UV absorber to the solvent butan-2-one. Once dissolved, 1,3,3- trimethylindolino-6 ' -nitrobenzopyrylospiran as photo-chromic material was added to the solution.
  • CAB-551-0.01, Foralyn 110, TegoGlide 410, tert-butyl ammonium nitrate, Joncryl682, butan-2-one and 1 , 3 , 3-trimethylindolino-6 ' - nitrobenzopyrylospiran are all commercially available.
  • the mixtures were left stirring for at least 2 hours, and then filtered through a GF/B (1.0 pm) filter.
  • the quantity of each component is provided in Table 5.
  • Inks 1, 2, and 3 were then printed by a CIJ printer as a rectangle on a polyethylene terephthalate (PET) substrate and a substrate made of PHBV-Enmat Y 1000, PEG400 and linalool (83:5:2 %wt ) .
  • PET polyethylene terephthalate
  • linalool 83:5:2 %wt
  • TTI ink 4 A further TTI ink (“Ink 4") was prepared by addition of CAB- 551-0.01 and Foralyn 110 as binders, TegoGlide 410 as additive, tert-butyl ammonium nitrate as salt, and
  • Joncryl682 as UV absorber to the solvent butan-2-one. Once dissolved, 1,3, 3-trimethylindolino-6 ' -nitrobenzopyrylospiran used as photo-chromic material was added to the solution.
  • CAB-551-0.01, Foralyn 110, TegoGlide 410, tert-butyl ammonium nitrate, Joncryl682, butan-2-one and 1,3,3- trimethylindolino-6 ' -nitrobenzopyrylospiran are all
  • Ink 2 (see Example 5) and Ink 4 were then compared.
  • the two inks were printed by a CIJ printer as a rectangle on a polyethylene terephthalate (PET) substrate.
  • PET polyethylene terephthalate
  • the graph ( Figure 7) shows that varying the concentration of the binder (polymer) or additives may affect the shelf-life of the TTI ink on a specific substrate.
  • the inks may therefore be tuned to foods or drinks having differing shelf-lives .
  • inks 1, 2 and 4 were compared on the same or differing substrates.
  • Figure 8 shows that similar shelf- lives for Inks 1, 2 and 4 can be achieved either on the same substrate (see Inks 1 and 4 on Figure 8) or on different substrates (see Inks 1 and 4 on PET and Ink 2 on PHBV- PEG400-linalool, Figure 8) despite the inks having differing compositions .

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

La présente invention concerne une encre pour impression jet d'encre comprenant un colorant photochromique et un absorbeur d'UV. Cette encre peut être utilisée en tant qu'indicateur de durée-température et se révèle particulièrement utile dans le cadre de l'emballage d'aliments et/ou de boissons pour fournir des indications relatives à la qualité du contenu.
PCT/GB2015/052618 2014-09-12 2015-09-10 Composition d'encre WO2016038373A1 (fr)

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JP2017534014A JP2017534740A (ja) 2014-09-12 2015-09-10 インク組成物
CN201580049288.4A CN107075287A (zh) 2014-09-12 2015-09-10 油墨组合物
US15/510,354 US10583666B2 (en) 2014-09-12 2015-09-10 Ink composition
EP15766210.7A EP3191555A1 (fr) 2014-09-12 2015-09-10 Composition d'encre

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GB1416165.7 2014-09-12
GB1416165.7A GB2534113B (en) 2014-09-12 2014-09-12 Ink composition

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JP2019034991A (ja) * 2017-08-10 2019-03-07 Dic株式会社 インク及び印刷物
FR3133924A1 (fr) 2022-03-24 2023-09-29 Psa Automobiles Sa Procede de detection et de marquage de defauts sur une piece et installation pour la mise en œuvre du procede

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KR102606962B1 (ko) * 2018-10-22 2023-11-29 리플스 엘티디 거품 음료 위에 프린팅하기 위한 제조 물품, 제제 및 방법
CN110105812A (zh) * 2018-10-24 2019-08-09 重庆理工大学 一种无油墨喷墨墨水及其制备方法和应用

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CN106280688A (zh) * 2016-08-08 2017-01-04 惠州市至上新材料有限公司 一种3c产品玻璃屏切割加工用的可碱溶的uv涂料及其制备方法
JP2019034991A (ja) * 2017-08-10 2019-03-07 Dic株式会社 インク及び印刷物
FR3133924A1 (fr) 2022-03-24 2023-09-29 Psa Automobiles Sa Procede de detection et de marquage de defauts sur une piece et installation pour la mise en œuvre du procede

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EP3191555A1 (fr) 2017-07-19
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US20170260412A1 (en) 2017-09-14
GB201416165D0 (en) 2014-10-29
US10583666B2 (en) 2020-03-10
JP2017534740A (ja) 2017-11-24
CN107075287A (zh) 2017-08-18

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